Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS5407982 A
Publication typeGrant
Application numberUS 08/155,395
Publication dateApr 18, 1995
Filing dateNov 19, 1993
Priority dateNov 19, 1993
Fee statusLapsed
Publication number08155395, 155395, US 5407982 A, US 5407982A, US-A-5407982, US5407982 A, US5407982A
InventorsCarlton E. Ash
Original AssigneeShell Oil Company
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Adding onium iodide salt of nitrogen, phosphorus, or arsenic
US 5407982 A
Abstract
It is herein disclosed a process for stabilizing freshly prepared polyketone polymer comprising contacting the polymer with a sufficient quantity of a stabilizing agent such as an alkali metal iodide salt or an onium iodide salt of nitrogen, phosphorus, or arsenic in which the organic groups comprising the cation coordination sphere is shielded by aromatic substituents. The inventive process results in stabilized polyketone polymers having and exhibiting improved thermal oxidative stability properties. It is also disclosed a stabilized polymer composition comprising a major amount of a polyketone polymer and a minor amount of an onium iodide salt of nitrogen, phosphorus, arsenic or combination thereof in which the cation coordination sphere is shielded by aromatic substituents.
Images(6)
Previous page
Next page
Claims(19)
What is claimed is:
1. A stabilized polymer blend comprising a major amount of linear polyketone polymer which is a linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon and a minor amount of an onium iodide salt of nitrogen, phosphorus, arsenic or combination thereof, in which the organic groups comprising the cation coordination sphere is shielded by aromatic substituents.
2. A blend as in claim 1 wherein said iodide salt is tetraphenylphosphonium iodide.
3. A blend as in claim 1 wherein said iodide salt is 5-methyl-3-(methylthio)-1,4-diphenyl-1-H-1,2,4-triazolium iodide.
4. A blend as in claim 1 wherein said iodide salt is an iodide salt of bis(triphenylphosphoranylidene)ammonium.
5. A blend as in claim 1 wherein said iodide salt is an insitu species of 4-iodophenyltriphenylphosphonium or 1,4-bis(triphenylphosphonium)benzene.
6. A blend as in claim 1 wherein said iodide salt is present in an amount of from 0.01 to 10 wt %.
7. A blend as in claim 1 further comprising a hindered phenol.
8. A blend as in claim 7 wherein said hindered phenol is octadecyl 3,5-di-tert. butyl-4-hydroxyhydrocinnamate.
9. A blend as in claim 7 wherein said hindered phenol is ethylene bis (oxyethylene) bis-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamate).
10. A process for producing a stabilized linear polyketone polymer which is a linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon comprising contacting said polymer with an onium iodide salt of nitrogen, phosphorus, arsenic or combination thereof, in which the cation coordination sphere is shielded by aromatic substituents.
11. A process as in claim 10 wherein said contacting of said iodide salt is by means of melt compounding.
12. A process as in claim 10 wherein the contacting of the iodide salt with the polymer is by means of in-situ generation of said salt.
13. A process as in claim 10 wherein said iodide salt is present in an amount of from 0.1 to 1 wt %.
14. A process as in claim 10 further comprising the addition of a hindered phenol.
15. A process as in claim 11 wherein said iodide salt is an insitu species of 4-iodophenyltriphenylphosphonium or 1,4-bis(triphenylphosphonium)benzene.
16. A stabilized polymer blend which is a linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon comprising a major amount of a polyketone polymer and a minor amount of an alkali metal iodide salt.
17. A blend as in claim 16 wherein said alkali metal iodide salt is potassium iodide.
18. A blend as in claim 17 wherein said potassium iodide is present in an amount of from about 0.1 to 1 wt %.
19. A blend as in claim 18 further comprising a hindered phenol.
Description
FIELD OF THE INVENTION

This invention generally relates to polyketone polymers. More particularly, this invention relates to stabilized polyketone polymers, and to a novel process for producing such stabilized polymers.

BACKGROUND OF THE INVENTION

Polymers of carbon monoxide and olefins generally referred to as polyketones are well known in the art. Of particular interest among polyketone polymers, is the class of linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon. This class of polymers is disclosed in numerous U.S. patents assigned to Shell Oil Company, exemplified by U.S. Pat. No. 4,880,865 which is herein incorporated by reference.

Although the properties of polyketone polymers are suitable for many applications, linear alternating polymers of carbon monoxide and at least one ethylenically unsaturated hydrocarbon do exhibit a deterioration of physical properties upon thermal oxidative degradation. This degradation is due to a chemical attack of atmospheric oxygen on the polymer chains and is characteristic of most, if not all organic polymers. Oxidation is typically autocatalytic and occurs as a function of heat and oxygen, hence the term thermal oxidative degradation. It is desirable to inhibit the deterioration of polymer properties by stabilizing the polymer toward the adverse effects of heat and oxygen. There are a large number of thermal oxidative stabilizers which are employed commercially to stabilize thermoplastic polymers against such degradation. However, many of the thermal stabilizers which are known to be effective with polyolefins, polyamides, polyacetals, polyacrylates, etc. are only marginally or not at all effective when employed with polyketone polymers. It would therefore be of advantage to provide polyketone polymers which demonstrate improved heat stability to extend their use in higher temperature applications.

SUMMARY OF THE INVENTION

It is a general object of this invention to provide a stabilized polyketone polymer.

It is a further object of this invention to produce an oxidatively stable polyketone polymer.

It is also an object of this invention to provide a process for producing an oxidatively stabilized polyketone polymer.

Accordingly, it is now provided a method for producing an oxidatively stabilized polyketone polymer, comprising contacting freshly produced polyketone polymer with an onium iodide salt of a Group 15 element such as nitrogen, phosphorus, arsenic, or combination thereof in which the cation coordination sphere is shielded by aromatic substituents. It is also provided an oxidatively stabilized blend comprising a major amount of polyketone polymer and a minor amount of an onium iodide salt of a Group 15 element such as nitrogen, phosphorus, arsenic, or combination thereof in which the cation coordination sphere is shielded by aromatic substituents.

The method of contacting the polymer with the iodide salt includes diffusion, melt blending, or by in-situ formation of the iodide salt.

DETAILED DESCRIPTION OF THE INVENTION

The materials useful in practicing this invention include a linear alternating polymer of carbon monoxide and at least one ethylenically unsaturated hydrocarbon (simply referred to as a polyketone polymer), an onium iodide salt of a Group 15 element of the Periodic Table of Elements such as nitrogen, phosphorus, arsenic, or combination thereof (henceforth sometimes referred to as iodide salt), and other common polymer additives. For instance, fillers, extenders, lubricants, pigments, plasticizers, and other polymeric materials can be added to the polyketone compositions being stabilized to improve or otherwise alter the properties of the compositions. In general, the practice of this invention involves suitably contacting sufficient quantities of the useful material to form a stabilized polyketone polymer composition.

The iodide salts (stabilizing agent(s)) of the present invention yield polyketone polymers with improved heat stability when the additive is adequately dispersed in the polymer matrix. Dispersion of the stabilizing agent(s)in the polymer can be accomplished by a variety of methods known to those skilled in the art. Such methods include a) melt compounding after contacting the stabilizing agent with polyketone polymer by powder mixing or solvent deposition, b) diffusion of the stabilizing agent into polymer articles using a solvent which has some miscibility with both polymer and the stabilizing agent, or c) in-situ generation of the stabilizing agent utilizing a polymer blend comprising of precursors which upon application of a sufficient amount of heat generates the stabilizing agent.

Thermal oxidative degradation of organic polymers relates to the deterioration of polymer properties due to the chemical reaction(s) between the polymer and atmospheric oxygen. While oxidation processes are complicated and mechanistic pathways of oxidation between different polymers may vary, oxidation is generally promoted by heat, often initiated by trace impurities such as metal ions or organic prodegradants, and characterized overall as autocatalytic in which carbon radicals and peroxyl radicals constitute key intermediates in the catalytic cycles. Consumption of oxygen by the polymer propagates the catalytic cycle and generates oxygenated species which either comprise part of the polymer or are evolved as gaseous products. These oxygenated species may further be prodegradative to the polymer. For example, hydroperoxides are not inherently stable and are capable of decomposing into new radicals, either thermally or catalyzed by trace impurities, which can then initiate additional oxidative cycles.

For polyketones it is believed that the thermal oxidative process involves the formation of oxygenates which under aging conditions cleave polymer chains and result in a reduction of molecular weight and a loss of polymer entanglement. Ultimately this results in a deterioration of polymer mechanical properties such as reduced impact strength, loss of elongation at break, and embrittlement. It would therefore be advantageous to stabilize the polyketone polymers towards these property losses either by reducing their overall rate of oxidation or reducing their rate of polymer chain scission.

This object is accomplished by adding through conventional methods such as melt blending, or non-conventional methods such as diffusion with a carrier such as water, or by in-situ formation of the stabilizing agent which is selected from the group consisting of onium iodide salts of a Group 15 element such as nitrogen, phosphorus, arsenic, or combination thereof in which the cation coordination sphere is shielded by aromatic substituents. The preferred such oniums are completely coordinated by an aryl substituent or are part of an aromatic ring. The useful iodide salts are exemplified by those listed in Table 1. Because not all iodide salts are useful in the practice of this invention, Table 1 also includes a list of some of the non-useful iodide salts. The contacting of the unstabilized polyketone polymer and the stabilizing agent in the manner previously disclosed results in a stabilized polymer.

                                  TABLE 1__________________________________________________________________________Stabilizing Iodide Salts                         Non-stabilizing Iodide                                            Salts__________________________________________________________________________Tetraphenylphosphonium                PPh4 +             ZnI2 - Zinc iodideBis(triphenylphosphoranylidene)                Ph3 PN+PPh 3  CaI2 - calcium                                            iodideammoniumInsitu 4-iodophenyltriphenyl- phosphonium 1,4-bis(triphenylphos- phonium)benzene                 ##STR1##                   Et4 NI                                            - tetraethylammonium                                            iodide                                            Me4 NI - tetra-                                            methylammonium idodide5-methyl-3-(methylthio-1,4-diphenyl 1H-1,2, 4-triazolium                 ##STR2##                   PPh3 MeI -                                            Methyltriphenyl-                                            phosphonium iodide9-phenanthryl triphenylphosphonium               PMe (OPh)3 I -                                            Methyltri-                                            phenoxyphosphonium                                            iodide                                            PPh4 Cl -                                            Tetraphenyl-                                            phosphonium chlorideKI (diffusion only)1                        PPh4 Br -                                            Tetraphenyl-                                            phosphonium__________________________________________________________________________                                            bromide 1 Other alkali metal iodide salts such as lithium, potassium, and sodium iodide are also within the scope of the invention.

The polymer of the invention, the inventive stabilizing agents, conventional additives typically useful in the formulation of the inventive composition, and a process for producing the stabilized polyketone polymer of the invention are discussed in more details in various sections of this specification.

The polyketone polymers which are employed as the major component of the oxidatively stabilized polymer composition of the invention are of a linear alternating structure and contain substantially one molecule of carbon monoxide for each molecule of ethylenically unsaturated hydrocarbon. The preferred polyketone polymers are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated hydrocarbon of at least 3 carbon atoms, particularly an α-olefin such as propylene.

When the preferred polyketone terpolymers are employed as the major polymeric component of the blends of the invention, there will be within the terpolymer at least about 2 units incorporating a moiety of ethylene for each unit incorporating a moiety of the second hydrocarbon. Preferably, there will be from about 10 units to about 100 units incorporating a moiety of the second hydrocarbon. The polymer chain of the preferred polyketone polymers is therefore represented by the repeating formula ##STR3## where G is the moiety of ethylenically unsaturated hydrocarbon of at least 3 carbon atoms polymerized through the ethylenic unsaturation and the ratio of y:x is no more than about 0.5. When copolymers of carbon monoxide and ethylene are employed in the compositions of the invention, there will be no second hydrocarbon present and the copolymers are represented by the above formula wherein y is zero. When y is other than zero, i.e. terpolymers are employed, the --CO--CH2 --H2) units and the --CO--G-- units are found randomly throughout the polymer chain, and preferred ratios of y:x are from about 0.01 to about 0.1. The precise nature of the end groups does not appear to influence the properties of the polymer to any considerable extent so that the polymers are fairly represented by the formula for the polymer chains as depicted above.

Of particular interest are the polyketone polymers of number average molecular weight from about 1000 to about 200,000, particularly those of number average molecular weight from about 20,000 to about 90,000 as determined by gel permeation chromatography. The physical properties of the polymer will depend in part upon the molecular weight, whether the polymer is a copolymer or a terpolymer, and in the case of terpolymers the nature of the proportion of the second hydrocarbon present. Typical melting points for the polymers are from about 175° C. to about 300° C., more typically from about 210° C. to about 270° C. The polymers have a limiting viscosity number (LVN), measured in m-cresol at 60° C. in a standard capillary viscosity measuring device, from about 0.5 dl/g to about 10 dl/g, more frequently from about 0.8 dl/g to about 4 dl/g.

A preferred method for the production of the polyketone polymers is illustrated by U.S. Pat. No. 4,834,144 which is herein incorporated by reference.

Broadly speaking, the process of the invention involves dispersing a sufficient amount of stabilizing agent into polyketone polymer to improve the thermal oxidative stability of the polymer. In general, the stabilizers of this invention are employed in an amount within the range of from 0.01 to about 10 percent based on the weight of the polyketone polymer, preferably in the range of from 0.1 to 1.0 percent based on the weight of polyketone polymer. The stabilizer may be incorporated into the polyketone polymer at any stage of its processing, preferably prior to being subjected to elevated temperature, or at such times as desired to improve thermal oxidative stability. The method of incorporating the stabilizer is not considered to be critical so long as the method results in a substantially uniform blend of the composition components. Such methods include a) melt compounding after contacting the stabilizing agent with polyketone polymer by powder mixing or solvent deposition, b) diffusion of the stabilizing agent into polymer articles using a solvent which has some miscibility with both polymer and the stabilizing agent, or c) in-situ generation of the stabilizing agent utilizing a polymer blend comprising of precursors which upon sufficient amount of heat generates the stabilizing agent.

After preparation, the now stabilized polyketone polymers show improved retention of desired mechanical properties, such as resistance to embrittlement when tested under conditions of elevated temperature and air exposure. The test as disclosed in U.S. Pat. No. 4,994,511 subjects polymer samples to aerobic oven aging at various temperatures and monitors the time until brittle failure (cracking) occurs when sharply bent at an angle of 180°.

As will be seen from the examples and data table disclosed herein, freshly prepared polyketone polymers comprising the inventive stabilizing agent and prepared according to the methods of this invention have and exhibit improved stability, particularly improved thermal oxidative stability.

The following examples and tables further illustrate the various aspects of the invention.

EXAMPLES

Polymers used in the following examples are described in Table 2. An oven aging test was used throughout the examples to distinguish the performance of polymer additives. In this test, polymer sheet of 20 or 30 mil thicknesses was prepared either by melt extrusion or compression molding. Test specimens were then cut into 1 cm wide strips and placed into forced air circulating ovens at 100° C. or 125° C. Periodically, the strips were withdrawn from the oven and when cooled bent to a 180-degree angle. When the samples became sufficiently brittle to break under this test procedure it was considered to be a failure and the time to embrittlement was recorded.

              TABLE 2______________________________________Polyketone polymers used in illustrative examples.   LVN     Tm               BasePolymer dl/g    °C.                   Form     Additivesb______________________________________A       1.95    220     Ext. Sheeta                            0.5% Irganox 1330                            0.5% Nucrel 535B       1.86    220     Ext. Sheeta                            0.2% Irganox 1330                            0.2% CaHApc                            0.3% Nucrel 535C       1.77    220     Powder   0.2% Irganox 1330                            0.2% CaHAp                            0.3% Nucrel 535D       1.73    220     Powder   0.2% Irganox 1330                            0.2% CaHAp                            0.3% Nucrel 535E       1.87    220     Powder   None______________________________________ a Extruded sheet of 20 mil thickness. b Percent based on weight of polyketone polymer. c Calcium Hydroxyapatite. "IRGANOX 1330" (a trademark of CibaGeigy Corp.) is 1,3,5trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene, "NUCREL 535" (a trademark of DuPontMitsui Polychemicals, Ltd.) i Poly(ethyleneco-methacrylic acid) with 1.0% acrylic acid content
EXAMPLES 1-5

Examples 1-5 demonstrate the utility of iodide additives to heat aging when diffusionally incorporated into polyketone polymer. Test specimens were prepared by immersing polymer A in the form of 20 mil sheet into a water composition for 20-25 min at a temperature of 90°-95° C. The water used was HPLC grade, OmniSolv® supplied by EM Science. Water compositions used in examples 2-5 included: water alone, 0.30 wt % ZnI2, 2.0% KI, and saturated Ph4 PI which is only sparingly soluble in water at 90°-95° C. After exposure, the polymer specimens were cooled, wiped clean of any surface residue, and dried in a vacuum oven at 50° C. with a nitrogen purge over night. One centimeter wide oven test strips were then cut from the exposed sheets. For the sample which was exposed to Ph4 PI, neutron activation tests were conducted to determine the iodide present in the polymer after this exposure. Residual iodine measured ca. 900 ppm, calculating to 0.33% Ph4 PI present in this sample. Results of oven aging tests are shown in Table 3.

              TABLE 3______________________________________Iodide additives diffusionally incorporated intopolyketone polymer.             Days to FailureExample     Exposure    125° C.                           100° C.______________________________________1           --          20      782           H2 O   22      813           H2 O/ZnI2                   21      834           H2 O/KI                   27      1215           H2 O/Ph4 PI                   45      234______________________________________

Examples 2 and 3 show that simply exposing the polymer sheet to water alone or to a solution of ZnI2 does not result in improved heat stability. Exposure to KI and Ph4 PI results in an improvement in heat stability with Ph4 PI being far superior in its ability to stabilize this polyketone polymer--greater than 2 times the control, Example 1.

EXAMPLES 6-10

Test specimens used in Examples 6-10 were diffusionally prepared and then tested as described in Examples 2-5 using polymer A and water compositions which contained 2.0% of the corresponding test additive. The results are summarized in Table 4.

              TABLE 4______________________________________Onium iodide salt additives diffusionally incorporatedinto polyketone polymer.              Days to FailureExample    Exposure      125° C.                            100° C.______________________________________6          --            24      1087          H2 O/Ph4 PBr                    21      1138          H2 O/Ph4 PCl                    25      1109          H2 O/Et4 NI                    26      11710         H2 O/Ph4 PI                    44      245______________________________________

Examples 7, 8, & 10 show that of the Ph4 P halide salts only the iodide is stabilizing to polyketone polymers. Example 9 demonstrates that alkyl ammonium iodides such as tetraethylammonium iodide (Et4 NI) are not effective in stabilizing polyketone polymers. This demonstrates that not all onium iodide salts are effective as stabilizers for polyketone polymer.

EXAMPLES 11-13

Examples 11-13 were prepared as described in Example 1-5 with the exception that extruded sheet of polymer B was used instead of polymer A. Test specimens for examples 12 & 13 were prepared similar to Examples 7-10. Oven aging results are shown in Table 5.

              TABLE 5______________________________________Comparison of iodide salts diffusionally added topolyketone polymer.             Days to FailureExample     Exposure    125° C.                           100° C.______________________________________11          --          18      9712          H2 O/CaI2                   19      9613          H2 O/Ph4 PI                   28      128______________________________________

These examples show once again that not all iodide salts are stabilizing to polyketone polymer. Calcium iodide shows no improvement in time to embrittlement over the control.

EXAMPLES 14-16

Examples 14-16 demonstrate that powder mixing of Ph4 PI and polyketone polymer followed by melt processing results in a polymer composition with improved thermal oxidative stability. Examples 15 and 16 were prepared by combining 100 grams polymer C powder with Ph4 PI powder and then homogenizing by tumbling overnight. Each mixture was then extruded on a 15 mm Baker-Perkins twin screw extruder operating at a melt temperature of about 250° C. The extruded compositions were then used to make plaques of 30 mil thicknesses by compression molding. As shown in Table 6, compositions with Ph4 PI showed significantly improved time to embrittlement at 125° C. over the control.

              TABLE 6______________________________________Aging performance of Ph4 PI melt blended into polyketonepolymer.                  Days to FailureExample     Additive   125° C.______________________________________14          --          815          0.25% Ph4 PI                  1816          0.50% Ph4 PI                  17______________________________________
EXAMPLES 17-26

Examples 17-32 compositions were prepared by melt processing as described in Examples 14-16 with the exception that polymer D was used instead of polymer C. Oven aging test results shown in Table 7, illustrate that onium iodide salts with alkyl substituents (ex. 18-22) exhibit no stabilizing influence on polyketone polymers. Examples 25 and 26 demonstrate the stabilizing influence of iodide salts other than Ph4 PI which also contain onium cations shielded by aromatic substituents, i.e. bis(triphenylphosphoranylidene)ammonium and a triazolium salt, respectively. In these examples, the increased stability was somewhat small, but similar in magnitude to the benefit from Ph4 PI in this polymer, Example 24.

              TABLE 7______________________________________Aging performance of onium iodide salts melt blendedinto polyketone polymer.               Days to FailureExample   Additive        125° C.                             100° C.______________________________________17        --              17      7318        0.43% Ph3 MePI                     16      4819        0.49% (PhO)3 MePI                     Not processable20        0.28% Et4 NI                     12      3021        0.50% Et4 NI                     12      3222        0.22% Me4 NI                     11      3023        --              2224        0.3% Ph4 PI                     2625        0.43% PPNIa                     2526        0.25% TIb  27______________________________________ a bis(triphenylphosphoranylidene)ammonium iodide b 5Methyl-3-(methylthio)-1,4-diphenyl-1H-1,2,4-triazolium iodide
EXAMPLES 27-39

Examples 27-39 compositions were prepared by melt processing as described in Examples 14-16 using the polymers and additives identified in Table 8. Example 30 demonstrates the improved resistance to embrittlement using only PPh4 I. Example 31 shows a significant improvement when a commercial hindered phenolic antioxidant such as Irganox 1076 is combined with Ph4 PI in polyketone polymers. This combination results in improved oven aging performance compared to using either individually. Examples 33-39 demonstrate that in-situ formation of phosphonium iodides from a phosphine and an organic iodide components improves the stability of polyketone polymer just as effectively as using Ph4 PI. Examples 34-37 shows that the use of either triphenyl phosphine or 1,4-diiodobenzene alone do not contribute to the stability of polyketone polymers. However, the combination of these additives in Example 33 yields a polymer with significantly improved heat aging performance. Examples 38 and 39, further show the beneficial effect when an organic iodide and triphenylphosphine are combined in the additive package.

              TABLE 8______________________________________Aging performance of phosphonium iodides melt blendedinto polyketone polymers and generated in-situ.                               Days to                               FailureExample  Polymer  Additive            125° C.______________________________________27     E        None                1528     E        0.5% Irganox 1076   1929     E        0.5% Irganox 245    2630     E        0.3% Ph4 PI    3831     E        0.5% Irganox 1076, 0.3% Ph4 PI                               4332     E        0.5% Irganox 245, 0.3% Ph4 PI                               3633     E        0.2% PPh3, 0.3% PhI2, 0.5%                               42           Irganox 24534     E        0.3% PPI2, 0.5% Irganox 245                               1135     D        --                  1836     D        0.2% PPh3      1337     D        0.3% PPH3      1538     E        0.5% Irganox 245, 0.3% 9-                               26           iodophenanthrene39     E        0.5% Irganox 245, 0.3% 9-                               38           iodophenanthrene, 0.2% PPh3______________________________________ "IRGANOX 1076" (a trademark of CibaGeigy Corp.) is Octodecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, "IRGANOX 245" (a trademark of CibaGeigy Corp.) is a Ethylenebis(oxyethylene)bis(3-tert-buthyl-4-hydroxy-5-methylhydrocinnamat

While this invention has been described in detail for the purpose of illustration, it is not to be construed as limited thereby but is intended to cover all changes and modifications within the spirit and scope thereof.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2599501 *Mar 23, 1949Jun 3, 1952Du PontReaction of phosphorus halides with monoolefin-carbon monoxide copolymers
US3422047 *Jan 19, 1966Jan 14, 1969American Cyanamid CoFlame retardant compositions for plastics
US3477986 *Apr 20, 1967Nov 11, 1969Bayer AgPolyamides stabilized with combination of a copper compound and a phosphonium halide
US3483260 *Oct 27, 1967Dec 9, 1969Ethyl CorpTetrakis - hydroxybenzyl phosphonium halides and the preparation thereof
US3530164 *Aug 13, 1965Sep 22, 1970American Cyanamid CoFlame retardant agents for thermoplastic products
US3532667 *May 31, 1967Oct 6, 1970Du PontPolyamides stabilized with phosphonium halides
US3547877 *Jul 1, 1968Dec 15, 1970American Cyanamid CoSynergistic flame-retardant compositions
US3553161 *Jun 11, 1968Jan 5, 1971Bayer AgPolyamides stabilized against degradation with copper salts and phosphine halides
US3635885 *Jul 28, 1969Jan 18, 1972Exxon Research Engineering CoPolyolefins stabilized with alkenyl phenols
US3642691 *Sep 19, 1969Feb 15, 1972Ethyl CorpTetrakis (hindered phenolic)phosphonium halide antioxidants
US3674854 *Jan 25, 1971Jul 4, 1972Exxon Research Engineering Co(3,5 dialkyl-4-hydroxy benzyl-)trialkyl phosphonium chlorides and corresponding zwitterions
US3676401 *Oct 30, 1970Jul 11, 1972Eastman Kodak CoEnvironmentally disintegratable plastic compositions comprising copolymers of ethylene and carbon monoxide and a degradation accelerator
US3681126 *Nov 18, 1970Aug 1, 1972Monsanto CoFlame retardant article containing tris-(3 - halo - 2-hydroxypropyl)-hydroxymethylphosphonium chloride
US3696078 *Aug 13, 1970Oct 3, 1972Monsanto CoAntistatic nylon filaments
US3770831 *Apr 5, 1972Nov 6, 1973Monsanto CoTris-(3-halo-2-hydroxypropyl)-hydroxymethylphosphonium chloride
US3776883 *Apr 3, 1972Dec 4, 1973Celanese CorpFlame retardant polyester compositions
US3968082 *Sep 9, 1974Jul 6, 1976Atlantic Richfield CompanyStabilized ethylene-carbon monoxide copolymers
US4139522 *Mar 13, 1978Feb 13, 1979Arco Polymers, Inc.Manganous salts of phosphorus oxy acids
US4452601 *Mar 19, 1982Jun 5, 1984Celanese CorporationTetrasubstituted phosphonium salts as promoters
US4761453 *Oct 13, 1987Aug 2, 1988Shell Oil CompanyPolymer processing
US4831083 *May 15, 1987May 16, 1989Ausimont S.R.L.Co-vulcanizable compositions of fluoroelastomers having improved chemical stability
US4843144 *Aug 26, 1987Jun 27, 1989Shell Oil CompanyPolymerization of carbon monoxide/olefin with P ligand having polar aryl group
US4880863 *Jun 27, 1988Nov 14, 1989Shell Oil CompanyPolymer blend
US4880865 *Aug 31, 1988Nov 14, 1989Shell Oil CompanyMolding materials
US4880903 *Aug 5, 1988Nov 14, 1989Shell Oil CompanyPolyketone from carbon monoxide and mixture of olefins
US4912171 *Aug 17, 1989Mar 27, 1990Minnesota Mining And Manufacturing CompanyBlend of addition polymer, polyhydroxy compound, organo-onium compound and acid acceptor
US4994511 *Oct 30, 1989Feb 19, 1991Shell Oil CompanyPolyketone stabilization with dihydrocarbyldithiocarbamate salts
US5008345 *May 18, 1990Apr 16, 1991Zeon Chemical Usa, Inc.Two-Part Curing System Containing A Metallic Acid Salt And An Ammonium Or Phosphonium Quaternary Salt
US5021473 *Nov 3, 1988Jun 4, 1991Hoechst AktiengesellschaftProcess for enhancing the electrostatic chargeability of powder coatings or powders, and the use thereof for surface-coating solid objects
US5041329 *Dec 4, 1990Aug 20, 1991Mitsui Petrochemical Industries, Ltd.Vulcanized rubber article and process for the preparation of the same
*DE176046C Title not available
EP0211431A2 *Aug 4, 1986Feb 25, 1987AUSIMONT S.p.A.Covulcanizable compositions of fluoroelastomers having improved chemical stability
EP0213671A1 *Aug 15, 1986Mar 11, 1987Shell Internationale Research Maatschappij B.V.New polymers of carbon monoxide and ethene
EP0326224A2 *Jan 24, 1989Aug 2, 1989Shell Internationale Research Maatschappij B.V.Polyketone copolymer composition
JPH03121150A * Title not available
JPS489240B1 * Title not available
JPS4219940B1 * Title not available
JPS5021067A * Title not available
JPS5147173A * Title not available
JPS5240553A * Title not available
JPS60152542A * Title not available
WO1985001056A1 *Aug 28, 1984Mar 14, 1985Gen ElectricPolymer blends containing ionomeric elastomers
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5929150 *Aug 4, 1998Jul 27, 1999Shell Oil CompanyPolyketone solvents
US5955019 *Aug 3, 1998Sep 21, 1999Shell Oil CompanySolution spinning polyketone fibers
US5977231 *Aug 18, 1998Nov 2, 1999Shell Oil CompanyPolyketone solvents
US7015303Aug 5, 1999Mar 21, 2006Asahi Kasei Kabushiki KaishaAn alkylene-carbon monoxide copolymer in a solvent comprising an aqueous solution of calcium salts and/or iron salts; use in a wet spinning process for fibers; low toxicity, excellent in incombustibity, spinning stability and solvent recoverability
US7223829Dec 15, 2005May 29, 2007Asahi Kasei Kabushiki KaishaPolyketone solution
EP1116752A1 *Aug 5, 1999Jul 18, 2001Asahi Kasei Kabushiki KaishaPolyketone solution
Classifications
U.S. Classification524/106, 524/154, 524/115, 524/177, 524/401, 524/122
International ClassificationC08K5/00
Cooperative ClassificationC08K5/0008
European ClassificationC08K5/00P
Legal Events
DateCodeEventDescription
Jun 17, 2003FPExpired due to failure to pay maintenance fee
Effective date: 20030418
Apr 18, 2003LAPSLapse for failure to pay maintenance fees
Nov 6, 2002REMIMaintenance fee reminder mailed
Oct 5, 1998FPAYFee payment
Year of fee payment: 4
Jan 17, 1995ASAssignment
Owner name: SHELL OIL COMPANY, TEXAS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ASH, CARLTON E.;REEL/FRAME:007309/0368
Effective date: 19950112